Processes for producing chlorofluorocarbon compounds using inorganic fluoride

ABSTRACT

Methods and systems for producing chlorofluorocarbon with an inorganic fluoride (e.g., germanium tetrafluoride (GeF 4 )) are disclosed herein.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to Provisional U.S. Patent ApplicationNo. 60/912,564, entitled “Processes for Production of HydrofluorocarbonUsing Inorganic Fluoride From Hexachloroethane,” Attorney Docket No.43883-8009US, filed May 4, 2007, the disclosure of which is incorporatedherein by reference in its entirety. This application is also related toU.S. patent application Ser. No. ______, entitled “Processes forProducing Halogenated Hydrocarbon Compounds Using Inorganic Fluoride”,Attorney Docket No. 43833-8014US, U.S. patent application Ser. No.______, entitled “Processes for Producing Hydrofluorocarbon CompoundsUsing Inorganic Fluoride”, Attorney Docket No. 43833-8011US, and U.S.patent application Ser. No. ______, entitled “Processes for ProducingHalocarbon Compounds Using Inorganic Fluoride”, Attorney Docket No.43833-8013US, the disclosures of which are incorporated herein byreference in their entirety

TECHNICAL FIELD

The present disclosure is related to processes for producing halocarboncompounds (e.g., chlorofluorocarbon compounds). In particular, thepresent disclosure is related to processes for producingchlorofluorocarbon compounds, such as1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113),1,1-dichloro-1,2,2-trifluoroethane (CFC-114a), and/or1-chloro-1,1,2,2,2-pentafluoroethane (CFC-115).

BACKGROUND

Chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) compoundshave been used as refrigerants, fire extinguishing agents, propellants,and solvents since the early twentieth century. However, CFC and HCFCare now believed to deplete the ozone layer of the earth via UV-promotedreactions. As a result, the U.S. Environmental Protection Agency hasalready banned the production and importation of certain CFC and HCFCproducts.

Internationally, the Montreal Protocol has set out plans for replacingCFC and HCFC compounds with hydrofluorocarbon (HFC) compounds. However,the cost of producing HFC compounds is considerably higher than that ofproducing CFC or HCFC compounds. Presently, industrial fluorinationprocesses for producing HFC are based on hydrogen fluoride (HF)fluorination of chlorocarbons. FIG. 1 presents examples of knownpotential multistep routes to produce CFC-113.

As illustrated in FIG. 1, HFC-125 can be produced with either1,1,2-trichloroethene (triclene) or 1,1,2,2-tetrachloroethene (perclene)using multistep processes. For example, HFC-125 can be produced by firstconverting either triclene or perclene into1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and then fluorinatingHCFC-123 to 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124). HFC-125 canthen be produced by performing chlorine-fluorine exchange on HCFC-124with hydrogen fluoride.

The processes for producing HFC-125 are more complex, both chemicallyand operationally, than those for CFC and HCFC compounds. Moreover, boththe triclene and perclene processes require disposing of hydrogenchloride (HCl) byproducts. Procedures and equipment are available toconvert some of the HCl byproducts into a chlorine (Cl₂) gas andsubsequently recycle the chlorine gas back into the production process.Nonetheless, this recycling operation adds to the cost of the overallHFC production process.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram illustrating potential routes to HFC-125and HFC-134a in accordance with the prior art.

FIG. 2 is a schematic diagram illustrating a system for producinghalocarbon compounds in accordance with an embodiment of the disclosure.

FIG. 3 is a flow chart illustrating a method for producing halocarboncompounds in accordance with an embodiment of the disclosure.

FIG. 4 is a schematic diagram illustrating a system for producinghalocarbon compounds in accordance with an embodiment of the disclosure.

FIG. 5 is a Fourier transform infrared (FTIR) scan of a reaction productprepared in accordance with an embodiment of the disclosure.

FIG. 6 is a gas chromatography of a reaction product prepared inaccordance with an embodiment of the disclosure.

FIG. 7 is a Fourier transform infrared (FTIR) scan of a reaction productprepared in accordance with another embodiment of the disclosure.

FIG. 8 is a Fourier transform infrared (FTIR) scan of a reaction productprepared in accordance with another embodiment of the disclosure.

DETAILED DESCRIPTION

Specific details of several embodiments of the disclosure are describedbelow with reference to processes for efficiently and cost-effectivelyproducing halogenated hydrocarbon compounds. The term “halocarboncompounds” generally refers to halogen-substituted (e.g., fluorine-,chlorine-, bromine-, and/or iodine-substituted) organic compoundscontaining only carbon and halogen. Examples of halocarbon compoundsinclude fluorocarbon compounds containing fluorine and carbon,chlorocarbon compounds containing chlorine and carbon, andchlorofluorocarbon compounds containing fluorine, chlorine, and carbon.Several other embodiments of the invention may have differentconfigurations, components, or procedures than those described in thissection. A person of ordinary skill in the art, therefore, willaccordingly understand that the invention may have other embodimentswith additional elements, or the invention may have other embodimentswithout several of the elements shown and described below.

One aspect of the present disclosure is directed to the use of aninorganic fluoride as a fluorinating agent for producingchlorofluorocarbon (CFC) compounds, in particular, CFC-113 (CCl₂FCClF₂).The following description uses germanium tetrafluoride (GeF₄) as anexample of an inorganic fluoride to show various embodiments of thefluorination reaction of the present disclosure for illustrationpurposes. However, a skilled artisan will appreciate that GeF₄ is merelyan example of an inorganic fluoride. Other inorganic fluoride for use inthe systems and processes can include at least one of brominetrifluoride (BrF₃), manganese tetrafluoride (MnF₄), sulfur tetrafluoride(SF₄), bromine pentafluoride (BrF₅), and tungsten hexafluoride (WF₆).

Another aspect of the present disclosure relates to producing CFC-113,CFC-114a, and/or CFC-115 by performing a chlorine-fluorine exchange onchlorocarbon compounds. In one embodiment, the present disclosurerelates to producing CFC-113 from 1,1,1,2,2,2-hexachloroethane (referredto as “hexachloroethane” hereinafter). The inventor has observed thatthe reaction described above has an unexpectedly high yield (about70%-75%) and a good selectivity toward CFC-113, CFC-114a, CFC-115,and/or other desired chlorocarbon compounds, as described in more detailbelow with reference to the experimental results.

A further aspect of the present disclosure is directed to using one ormore catalysts to catalyze a fluorination reaction between an inorganicfluoride and a chlorocarbon compound. It is believed that, in certainembodiments, the class of compounds known as superacids and/or Lewisacids can catalyze such fluorination reaction. The term “superacid”generally refers to an acid with an acidity greater than that of 100%sulfuric acid (H₂SO₄). Examples of superacids include trifluoromethanesulfonic acid (CF₃SO₃H) and fluorosulfuric acid (FSO₃H). The term “Lewisacid” generally refers to a compound that is an electrophile or anelectron acceptor. Examples of Lewis acids include aluminum trichloride(AlCl₃), iron trichloride (FeCl₃), boron trifluoride (BCl₃), niobiumpentachloride (NbCl₅), and the lanthanide triflates, e.g.,ytterbium(III) triflate. In certain embodiments, aluminum trichloride(AlCl₃) can be used to react with GeF₄ to form AlCl_(x)F_(y) (x+y=3), insitu, which has been observed to catalyze the GeF₄ fluorination ofchlorocarbons. In other embodiments, SbCl₃, SbF₅, SbF₃, AsF₅, AsCl₃,TaCl₅, TaF₅, NbCl₅, NbF₅, HSO₃F, CF₃SO₃F, Cr₂O₃, and/or other suitablesuperacids and/or Lewis acids can also be used to catalyze afluorination of chlorocarbons in the presence of, e.g., GeF₄.

Reaction Systems

FIG. 2 is a schematic diagram illustrating a system 100 for producinghalocarbon compounds in accordance with an embodiment of the disclosure.The system 100 can include a reactor 101 operatively coupled to a feedstorage 104 containing, e.g., hexachloroethane, and an inorganicfluoride storage 106 containing, e.g., GeF₄. The reactor 101 can beconfigured generally as a tubular reactor constructed from Inconel,Hastelloy, and/or other fluorine-resistant material. In someembodiments, the reactor 101 can include a catalyst bed 102 containingAlCl₃ or other suitable catalyst. In other embodiments, the catalyst bed102 can be omitted from the reactor 101, and a catalyst (e.g., AlCl₃)can be fed into the reactor 101 during operation.

The system 100 can include a scrubber 108 that receives a reactionproduct from the reactor 101. The scrubber 108 can be configured toremove impurities and/or unreacted material from the product. Forexample, in one embodiment, the scrubber 108 includes a liquid basecontaining, e.g., potassium hydroxide (KOH), sodium hydroxide (NaOH),and/or other bases for absorbing, reacting, and/or otherwise combiningwith unreacted inorganic halide (e.g., GeF₄). In another embodiment, thescrubber 108 includes a solid base (e.g., pellets) containing KOH, NaOH,and/or other bases. In further embodiments, the scrubber 108 can includeboth a liquid base and a solid base for removing unreacted halides.

The system 100 can also include an optional product trap 110 downstreamof the scrubber 108 for collecting CFC and/or other compounds in thereaction product. In the illustrated embodiment, the product trap 110 isconfigured as a heat exchanger that can cool the reaction product with acoolant (e.g., liquid nitrogen). In some embodiments, heat exchange withthe coolant substantially condenses the CFC and/or other compounds inthe reaction product. In other embodiments, only a portion of the CFCand/or other compounds (e.g., materials with low boiling points) iscondensed.

The system 100 can further include a separator 112 downstream of theoptional product trap 110. The separator 112 can be configured to splitCFC and/or other compounds in the reaction product. In the illustratedembodiment, the separator 112 includes a distillation column that canproduce a first product from a top end 114 and a second product from abottom end 116. In other embodiments, the separator 112 can also includea flash tank, a cyclone, and/or other liquid-liquidseparation/liquid-gas separation devices. In further embodiments,instead of producing the first and second products from the top end 114and the bottom end 116, the separator 112 can also produce products fromlocations intermediate the top end 114 and the bottom end 116 based onthe volatility profile of the reaction product.

In operation, the reactor 101 first receives a reaction feed containing,for example, hexachloroethane from the feed storage 104 and an inorganicfluoride (e.g., GeF₄) from the inorganic fluoride storage 106. In oneembodiment, GeF₄ can be in the stoichiometric amount required tofluorinate hexachloroethane in the reaction feed. For example, the molarratio of GeF₄ to hexachloroethane can be about 1.16:1. In otherembodiments, GeF₄ can be in molar excess of the stoichiometric amountrequired. For example, the molar ratio of GeF₄ to hexachloroethane inthe reaction feed can be from about 2:1 to about 4:1.

In the reactor 101, GeF₄ and hexachloroethane in the reaction feedcontact the catalyst (e.g., AlCl₃) held in the catalyst bed. The reactor101 can be at a temperature of about 220° to about 375° C. and at apressure of about 500 to 800 psig (i.e., about 3.45 MPa to about 5.52MPa). In one embodiment, the inventor has observed that hexachloroethaneand GeF₄ in the reaction feed can react to form CFC-113 with high yieldand good selectivity at a reaction temperature of about 310° C. and amolar ratio of hexachloroethane to GeF₄ of about 1:1.67. Other potentialfluorination products can include 1,1,1-trichloro-2,2,2-trifluoroethane(CFC-113a), 1,2-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a),1-chloro-1,1,2,2,2-pentafluoroethane (CFC-115), and/or otherfluorine-substituted chloroethanes. In another embodiment, the inventorhas observed that hexachloroethane and GeF₄ in the reaction feed canreact to form CFC-114a (about 73%) and CFC-115 (about 27%) at a reactiontemperature of about 340° C. and a molar ratio of hexachloroethane toGeF₄ of about 1:2.75.

There have been prior unsuccessful attempts to use GeF₄ for fluorinationof chlorocarbons such as hexachloroethane. The inventor has recognizedthat those prior experiments failed, at least in part, because of theomission of an appropriate catalyst. The inventor has also recognizedthat AlCl₃ and/or other Lewis acid catalysts can cause GeF₄ to readilyreact with hexachloroethane. Without being bound by theory, it isbelieved that GeF₄ can first react with AlCl₃ to form a series ofequilibria between AlCl₃ and GeF₄ as follows:

AlCl₃+GeF₄

AlCl₂F+GeF₃Cl

AlClF₂+GeF₂Cl₂

AlF₃+GeFCl₃

It is believed that the AlCl_(x)F_(y) (x+y=3) compounds may then act asLewis acid catalysts to lower the activation energy for fluorinatinghexachloroethane. It is also believed that AlF₃ is a more efficientcatalyst than AlCl₂F and/or AlClF₂. Thus, in some embodiments, thereaction equilibria can be shifted toward AlF₃ by, for example, addingexcess GeF₄ to the reaction feed, removing products from the reaction,and/or using other suitable techniques.

In one embodiment, the reaction described above can be carried out in abatch mode. For example, the reaction conditions can be maintained inthe reactor 101 until the reaction is complete, and then the reactionproduct can be discharged from the reactor 101 to the scrubber 108. Inother embodiments, the reaction described above can be carried out in acontinuous mode. For example, the reactor 101 can be configured as aplug-flow reactor, a constantly stirred tank reactor, and/or other typesof reactor with sufficient residence time to allow the completion of thereaction in a continuous operation.

After the reaction is complete, the reaction product flows from thereactor 101 to the scrubber 108 for removing impurities and/or unreactedmaterial from the product. For example, the scrubber 108 can removegermanium tetrachloride (GeCl₄) from other gaseous material in thereaction product. In another example, if GeF₄ is in molar excess ofhexachloroethane in the reaction feed, some GeF₄ is likely to remainafter the reaction is complete. In one embodiment, the scrubber 108 cancontain KOH and/or NaOH that reacts with the excess GeF₄ in order topurify the reaction product. In other embodiments, the scrubber 108 canremove the excess GeF₄ using other physical and/or chemical techniques.

The reaction product can then pass through the optional product trap 110for collecting CFC and/or other compounds. In the illustratedembodiment, the reaction product exiting the scrubber 108 can include agas containing CFC-113, CFC-113a, CFC-114a, and/or CFC-115. When thereaction product passes through the product trap 110, CFC-113, CFC-113a,CFC-114a, CFC-115, and/or other chlorocarbon compounds in the reactionproduct can be substantially condensed by a coolant (e.g., liquidnitrogen). In other embodiments, the product trap 110 can include arefrigeration unit, an isotropic expander, an isenthalpic expander,and/or other cooling techniques for condensing the chlorocarboncompounds in the reaction product. In further embodiments, the system100 can operate at a sufficient pressure (e.g., 1000 psig) such that thereaction product is at least partially a liquid at the outlet of thescrubber 108, and the product trap 110 can be omitted.

After the reaction product is substantially condensed, the separator 112splits various chlorocarbon compounds (e.g., CFC-113) from others in thereaction product. In one embodiment, the separator 112 can produce thefirst product containing essentially CFC-113 from the top end 114 andthe second product containing other CFC compounds (e.g., CFC-113a) fromthe bottom end 116. In another embodiment, the separator 112 can producethe first product containing CFC-115 and the second product containingCFC-114a. At one atmospheric pressure, CFC-113 has a boiling point ofabout 4° C., and CFC-113a has a boiling point of about 45.8° C. CFC-114aand CFC-115 have boiling points of about −73° C. and about −36° C.,respectively. As a result, the relative volatility between CFC-113a andCFC-113 and that between CFC-114a and CFC-115 are sufficient to enable aready separation of these two compounds.

Fluorination reaction carried out in the system 100 described above canefficiently and cost-effectively produce desired chlorocarbon compounds(e.g., CFC-113, CFC-114a, CFC-115, and/or other chlorofluorocarboncompounds) that can be used as precursors for producing HFC and/or HCFCcompounds such as HFC-125 and HFC-134a. Unlike conventional techniques,using the system 100 can produce these chlorocarbon compounds via directchlorine-fluorine exchange on hexachloroethane. The reaction has beenobserved to produce an unexpectedly high yield of at least about 70%,more preferably at least about 75%, and even more preferably at leastabout 80%. In one embodiment, the reaction has also been observed toproduce a good selectivity toward CFC-113. In another embodiment, thereaction has been observed to produce a good selectivity toward CFC-114aof at least about 1.6, more preferably about 2.7, and even morepreferably about 4.0. Moreover, the reaction, in one embodiment, hasbeen observed to produce only CFC-114a and CFC-115, which havesufficiently different volatilities to enable ready separation of thereaction product.

Even though the system 100 described above has a one-pass configuration,in certain embodiments, the system 100 can also have at least onerecycle loop. For example, in some embodiments, unreacted reaction feedand/or other compounds can be recycled back to the reactor 101.

Method for Producing Halocarbon Compounds

FIG. 3 is a flow chart illustrating a method 200 for producinghalocarbon compounds (e.g., CFC-113, CFC-114a, and CFC-115) inaccordance with an embodiment of the disclosure. The method 200 caninclude contacting a reaction feed containing a chlorocarbon compound(e.g., hexachloroethane) with a metal halide (e.g., GeF₄) in thepresence of a catalyst (e.g., AlCl₃) at block 202. The molar ratio ofAlCl₃/hexachloroethane/GeF₄ can be about 1:A:B (6<A<15 and 7<B<60). Inone embodiment, the method 200 then includes performing a fluorinationreaction (e.g., a chlorine-fluorine exchange reaction) onhexachloroethane at block 204 as follows:

In another embodiment, the fluorination reaction can also be as follows:

Suitable reaction temperatures can be about 220° to about 375° C., andsuitable pressures can be about 500 to 800 psig.

A decision is made at block 206 to determine whether the reaction iscomplete. In one embodiment, the decision can be based on a reactiontime (e.g., about six to eight hours). In another embodiment, thedecision can be based on a conversion of the reaction and/or otherreaction parameters. For example, an operator can periodically samplethe material in the reactor 101 to determine a concentration ofhexachloroethane. If the concentration of hexachloroethane is below athreshold, then the reaction is indicated to be complete.

If the reaction is complete, the method 200 further includes purifyingthe reaction product at block 208. Purifying the reaction product caninclude separating desired CFC compounds of the reaction product usingcondensation, distillation, liquid-liquid extraction, liquid-gasseparation, and/or other suitable techniques. If the reaction is notcomplete, the process reverts to performing the chlorine-fluorineexchange on hexachloroethane at block 204.

EXAMPLES

Experiments were conducted to fluorinate hexachloroethane using GeF₄ inthe presence of AlCl₃ in a bench-top reactor (Model No. 4563) suppliedby the Parr Instrument Company of Moline, Ill. FIG. 4 is a schematicdiagram illustrating an experimental system 300 for producing halocarboncompounds in accordance with an embodiment of the disclosure.

As shown in FIG. 4, the system 300 includes an Inconel 600 reactor 302having a volume of about 600 mL. The reactor 302 includes a pressuremonitor 304, a mixer 306, and a temperature monitor 308. The reactor 302also includes a liquid sample line 310 and a gas sample line 312. Thesystem 300 also includes a cylinder 314 holding gaseous GeF₄ (187 psigat 21° C.). The system 300 also includes a 200 mL wet scrubber 316containing KOH and a desiccant vessel 318 containing Al₂O₃ and KOHpellets. The system 300 further includes three 75 mL sample cylinders320 (labeled C₁-C₃). The sample cylinders 320 can be held at varioustemperatures and pressures for collecting materials with differentboiling points. Various components of the system 300 can be isolatedusing a plurality of valves 322 (labeled V₁-V₁₉).

All chemicals used in the following experiments were obtainedcommercially from Aldrich-Sigma, Inc. of Milwaukee, Wis. The GeF₄ gaswas produced by International Isotopes Inc. of Idaho Falls, Id. Fouriertransform infrared (FTIR) spectra were recorded on a MIDAC I1201bench-top infrared spectrometer as neat liquids between potassiumbromide (KBr) plates or gas samples in a 10 cm path-length demountablegas cell with zinc-selenium (ZnSe) windows. 1H, 13C, and 19F NMR spectrawere obtained on a 300 MHz Bruker AMX spectrometer at 200, 50, and 188MHz, respectively, by using CDCl₃ as a locking solvent. Chemical shiftswere reported relative to Me₄Si or CFCl₃. GCMS spectra were obtainedwith a Shimadzu Q5050 spectrometer (El-mode). Elemental analyses wereperformed by the Desert Analytics Laboratory of Tucson, Ariz.

Experiment I

Solid hexachloroethane (44.5 g, 0.190 mol) and solid aluminum chloride(4.0 g, 0.030 mol) were charged into the reactor 302. The reactor 302was then closed and bolted. Germanium tetrafluoride (32.3 g, 0.217 mol)was fed into the reactor 302 at 19° C. in a vented hood. The pressure inthe reactor 302 was 130 psig. The gas-in and gas-out valves on thereactor 302 were closed to isolate the contents in the reactor 302, andthe supply sample line was purged several times and disconnected. Thereactor 302 was then transferred into a heating mantle and connectedonto a manifold with the scrubber 316, the desiccant vessel 318, and thesample cylinders 320 for cryogenic distillation. The contents in thereactor 302 were stirred and heated to about 220° C. for about one hour,about 250° C. for about one hour, and at 310° C. for about six hours.The reactor pressure rose to about 518 psig at 310° C. After eighthours, the reactor 302 was slowly cooled to room temperature(approximately 15° C.), and the pressure dropped to about 47 psig. Thegaseous reaction products, including unreacted GeF₄, were vented throughthe gas-out valve to the scrubber 316 until the pressure in the reactor302 dropped to about 0 psig. Germanium halide byproducts were recoveredas insoluble germanium (IV) oxide. Subsequently, the reactor 302 waspressurized several times with nitrogen to about 90 psig and ventedthrough the scrubber 316. Subsequently, the reactor 302 was pressurizedseveral times with nitrogen, to 90 psig, and vented through the scrubber316. Thereafter, the reactor 302 was opened in a vented hood. About 56.6grams of liquid were poured from the reactor 302 into a 100 mL highdensity polyethylene (HDPE) plastic container. About 5 grams of brownsolid residue were observed around the bottom of the reactor 302. Theliquid product was poured into 60 mL of deionized water in apolypropylene separating funnel. About 26.3 grams of non-fuming lightbrown liquid were separated and dried with 4 grams of magnesium sulfate(MgSO₄) in a 100 mL glass flask and then analyzed by FTIR, 19F NMR, andGCMS.

Experiment II

Experiment II was carried out following a procedure similar to that ofExperiment I with a different molar ratio of the reagents and adifferent reaction temperature than those used in Experiment I. Inparticular, solid hexachloroethane (30.2 g, 0.127 mol) and solidaluminum chloride (4.0 g, 0.030 mol) were charged into the reactor 302,and a reaction temperature of 340° C. was used. GeF₄ gas (49.5 g, 0.333mol) was then fed into the reactor 302. The reactor 302 was then heatedto 340° C., and the pressure in the reactor 302 rose to about 747 psig.After about eight hours, the reactor 302 was slowly cooled to roomtemperature. As a result, the pressure dropped to about 110 psig atabout 21° C.

Experimental Results

In Experiment I and Experiment II, hexachloroethane reacted readily withGeF₄ in the presence of a superacid and/or a Lewis acid catalyst. Asshown in the FTIR analysis and gas chromatography results in FIGS. 5 and6, the reaction product in Experiment I contained about 53% CFC-113. Theidentification of the isomer product was based on the correlation of thecoupling constant of the triplet and doublet signals in the ¹⁹F NMRspectrum of the reaction product. The gaseous product did not havecharacteristics of any expected fluorocarbon products. The conversion ofhexachloroethane was about 75%. As shown in the FTIR analyses in FIGS. 7and 8, the reaction product in Experiment II contained about 73%CFC-114a, and about 27% CFC-115. The conversion of hexachloroethane wasabout 98%

From the foregoing, it will be appreciated that specific embodiments ofthe invention have been described herein for purposes of illustration,but that various modifications may be made without deviating from theinvention. Elements of one embodiment may be combined with otherembodiments in addition to or in lieu of the elements of the otherembodiments. Accordingly, the invention is not limited except as by theappended claims.

1. A method for producing chlorofluorocarbon compounds, comprisingreacting 1,1,1,2,2,2-hexachloroethane (Cl₃CCCl₃) with germaniumtetrafluoride (GeF₄) in the presence of a metal halide.
 2. The method ofclaim 1 wherein reacting 1,1,1,2,2,2-hexachloroethane with germaniumtetrafluoride includes reacting 1,1,1,2,2,2-hexachloroethane withgermanium tetrafluoride in the presence of aluminum trichloride (AlCl₃).3. The method of claim 2 wherein reacting 1,1,1,2,2,2-hexachloroethanewith germanium tetrafluoride includes reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride in thepresence of aluminum trichloride at a temperature of about 220° to about375° C.
 4. The method of claim 2, further comprising forming at leastone of aluminum chlorodifluoride (AlClF₂), aluminum dichlorofluoride(AlCl₂F), and aluminum trifluoride (AlF₃) when reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride.
 5. The methodof claim 4, further comprising shifting the equilibrium toward aluminumtrifluoride.
 6. The method of claim 2 wherein reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride includesreacting 1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride at amolar ratio of germanium tetrafluoride to 1,1,1,2,2,2-hexachloroethaneof about 1.16 to
 1. 7. The method of claim 2, further comprisingproducing at least one of 1,1,2-trichloro-1,2,2-trifluoroethane(CCl₂FCClF₂), 1,1,1-trichloro-2,2,2-trifluoroethane (CCl₃CF₃),1,2-dichloro-1,2,2,2-tetrafluoroethane (CCl₂FCF₃), and1-chloro-1,1,2,2,2-pentafluoroethane (CClF₂CF₃) by reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride.
 8. A methodfor producing chlorofluorocarbon compounds, comprising contacting areaction feed containing 1,1,1,2,2,2-hexachloroethane (Cl₃CCCl₃) andgermanium tetrafluoride (GeF₄) with a catalyst containing a metal halidein a reactor, to thereby produce a reaction product containing at leastone of 1,1,2-trichloro-1,2,2-trifluoroethane (CCl₂FCClF₂) and1,1,1-trichloro-2,2,2-trifluoroethane (CCl₃CF₃).
 9. The method of claim8 wherein contacting a reaction feed includes contacting the reactionfeed with a catalyst bed of the reactor, the catalyst bed holding acatalyst containing aluminum trichloride (AlCl₃).
 10. The method ofclaim 8 wherein reacting 1,1,1,2,2,2-hexachloroethane with germaniumtetrafluoride includes performing chlorine-fluoride exchange on1,1,1,2,2,2-hexachloroethane of the reaction feed in the presence of thecatalyst.
 11. The method of claim 8 wherein reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride includesreacting 1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride at atemperature of about 220° C. to about 375° C. and a pressure of about500 to about 800 psig.
 12. The method of claim 8 wherein the metalhalide includes aluminum trichloride (AlCl₃), and wherein reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride includesreacting 1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride at amolar ratio of aluminum chloride/1,1,1,2,2,2-hexachloroethane/germaniumtetrafluoride of about 1:6:7.
 13. The method of claim 8 wherein reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride includesreacting 1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride whilegermanium tetrafluoride is in molar excess over1,1,1,2,2,2-hexachloroethane, and wherein the method further includesscrubbing excess germanium tetrafluoride with a material containing abase.
 14. The method of claim 8, further comprising distilling theproduced reaction product containing at least one of1,1,2-trichloro-1,2,2-trifluoroethane (CCl₂FCClF₂) and1,1,1-trichloro-2,2,2-trifluoroethane (CCl₃CF₃).
 15. A method forproducing chlorofluorocarbon compounds, comprising: loading a chargecontaining 1,1,1,2,2,2-hexachloroethane (Cl₃CCCl₃) and aluminumtrichloride (AlCl₃) into a reactor; flowing a feed gas containinggermanium tetrafluoride (GeF₄) into the reactor holding the chargecontaining 1,1,1,2,2,2-hexachloroethane (Cl₃CCCl₃) and aluminumtrichloride; and reacting 1,1,1,2,2,2-hexachloroethane of the chargewith germanium tetrafluoride of the feed gas in the presence of aluminumtrichloride in the reactor.
 16. The method of claim 15, furthercomprising discharging a product containing at least one of1,1,2-trichloro-1,2,2-trifluoroethane (CCl₂FCClF₂) and1,1,1-trichloro-2,2,2-trifluoroethane (CCl₃CF₃) from the reactor. 17.The method of claim 16, further comprising collecting the product in acylinder cooled with liquid nitrogen.
 18. The method of claim 15,further comprising heating the reactor to a temperature of about 220° C.to about 375° C. before flowing the feed gas into the reactor.
 19. Themethod of claim 15 wherein reacting 1,1,1,2,2,2-hexachloroethane of thecharge with germanium tetrafluoride of the feed gas includes reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride with aconversion greater than about 70%.
 20. The method of claim 15 whereinreacting 1,1,1,2,2,2-hexachloroethane of the charge with germaniumtetrafluoride of the feed gas includes reacting1,1,1,2,2,2-hexachloroethane with germanium tetrafluoride with aconversion greater than about 70% and a selectivity greater than about50% for 1,1,2-trichloro-1,2,2-trifluoroethane (CCl₂FCClF₂).
 21. A methodfor producing chlorofluorocarbon compounds, comprising: contacting afirst reagent containing 1,1,1,2,2,2-hexachloroethane (Cl₃CCCl₃) with asecond reagent containing germanium tetrafluoride (GeF₄) in the presenceof a catalyst containing aluminum trichloride (AlCl₃); concurrentlyforming a series of equilibria between species of AlCl_(x)F_(y) (x+y=3)and species of GeCl_(a)F_(b) (a+b=4), as follows:AlCl₃+GeF₄←→AlCl₂F+GeF₃Cl←→AlClF₂+GeF₂Cl₂←→AlF₃+GeFCl₃ fluorinating1,1,1,2,2,2-hexachloroethane in the first reagent with germaniumtetrafluoride in the second reagent while catalyzed by the species ofAlCl_(x)F_(y) (x+y=3).
 22. The method of claim 21 wherein fluorinating1,1,1,2,2,2-hexachloroethane includes shifting the series of equilibriato produce a product from the reaction with a selectivity toward atleast one of 1,1,2-trichloro-1,2,2-trifluoroethane (CCl₂FCClF₂),1,1-dichloro-1,2,2-trifluoroethane (CCl₂FCHF₂), and1-chloro-1,1,2,2,2-pentafluoroethane (CClFCF₃).
 23. The method of claim21 wherein performing a reaction includes performing a reaction between1,1,1,2,2,2-hexachloroethane in the first reagent and germaniumtetrafluoride in the second reagent while catalyzed by the species ofAlCl_(x)F_(y) (x+y=3) at a temperature of about 310° C. and a molarratio of 1,1,1,2,2,2-hexachloroethane to germanium tetrafluoride ofabout 1:1.67, and wherein selectively producing a product includesproducing a product containing at least about 50%1,1,2-trichloro-1,2,2-trifluoroethane (CCl₂FCClF₂).
 24. The method ofclaim 21 wherein performing a reaction includes performing a reactionbetween 1,1,1,2,2,2-hexachloroethane in the first reagent and germaniumtetrafluoride in the second reagent while catalyzed by the species ofAlCl_(x)F_(y) (x+y=3) at a temperature of about 340° C. and a molarratio of 1,1,1,2,2,2-hexachloroethane to germanium tetrafluoride ofabout 1:2.75, and wherein selectively producing a product includesproducing a product substantially consisting of1,1-dichloro-1,2,2-trifluoroethane (CCl₂FCHF₂) and1-chloro-1,1,2,2,2-pentafluoroethane (CClFCF₃).
 25. The method of claim21 wherein performing a reaction includes performing a reaction between1,1,1,2,2,2-hexachloroethane in the first reagent and germaniumtetrafluoride in the second reagent while catalyzed by the species ofAlCl_(x)F_(y) (x+y=3) at a temperature of about 340° C. and a molarratio of 1,1,1,2,2,2-hexachloroethane to germanium tetrafluoride ofabout 1:2.75, and wherein selectively producing a product includesproducing a product containing about 73%1,1-dichloro-1,2,2-trifluoroethane (CCl₂FCHF₂) and about 23%1-chloro-1,1,2,2,2-pentafluoroethane (CClFCF₃).